Stabilizer composition

ABSTRACT

The invention relates to novel compositions of photoreactive, UV-light absorbing, low molecular weight polyalkylpiperidines and non-photoreactive low molecular weight sterically hindered polyalkylpiperidines as well as to masterbatch compositions comprising the novel compositions. The invention relates further to a process for enhancing the light stability of organic material, the stabilized organic material and its use.

The invention relates to novel compositions of photoreactive, lowmolecular weight polyalkylpiperidines and non-photoreactive lowmolecular weight sterically-hindered polyalkylpiperidines as well as tomasterbatch compositions comprising the novel compositions and a processfor stabilizing natural or synthetic organic polymeric or prepolymericsubstrates against the damage effected by light, heat and/or oxidation.The invention also relates to the corresponding stabilized organicmaterial and its use in the production of fibers and yarn, moldings,foamed plastic, coatings, lacquers or varnishes, adhesives and fabric.

According to the invention there is provided a composition, particularlysuitable as light stabilizer, consisting of a photoreactive, UV-lightabsorbing, low molecular weight polyalkylpiperidines of general formulaI (hereinafter referred to as component A) ##STR1## wherein R₁ signifieshydrogen, hydroxyl, C₁₋₂₀ alkyl, C₁₋₂₀ alkoxy, or alkyl

R₂ signifies hydrogen, C₁₋₈ alkyl, C₁₋₂ alkoxy

and a non-photoreactive, low molecular weight sterically hinderedpolyalkylpiperidine (hereinafter referred to as component B) selectedfrom the group consisting of the compounds B-1 to B-24 of the followinggeneral formulae

    R.sub.3 --OC(O)--(CH.sub.2).sub.n --C(O)O--R.sub.3         B- 1

    R.sub.3 --NH--(CH.sub.2).sub.n --NH--R.sub.3               B- 2

    R.sub.3 --OCH.sub.2 CH═CHCH.sub.2 --O--R.sub.3         B- 3

    R.sub.3 --OC(O)--NR.sub.3 --(CH.sub.2).sub.6 --NR.sub.3 C(O)O--R.sub.3B- 4

    R.sub.3 --O--Si(CH.sub.3).sub.2 --O--R.sub.3               B- 5

wherein

R₃ signifies a group selected from the group consisting of (a) to (g)##STR2## wherein alkyl signifies linear or branched or cyclic saturatedC₁₋₈ alkyl group or linear or branched or cyclic C₁₋₁₈ unsaturated group(alkenyl group)

n is an integer selected from 0 to 20, preferably 1-14, more preferably1-10. ##STR3## wherein R₄ signifies hydrogen, C₁₋₂₀ alkyl, preferablyC₁₋₁₀ alkyl, more preferably C₁₋₄ alky, or ##STR4## X signifies oxygen,N--R₄ ##STR5## wherein R₅ signifies hydrogen, C₁₋₂₀ alkyl, hydroxyl,C₁₋₂₀ alkoxy, acyl

R₆ signifies hydrogen, C₁₋₂₀ alkyl, --CH₂ ##STR6## (CH₂)_(m) COOR₇,wherein m is an integer selected from 0 to 10, preferably 0-2, and

R₇ is C₁₋₂₀ alkyl ##STR7##

    R.sub.3 --NH--C(O)--(CH).sub.n --C(O)--NH--R.sub.3         B- 12

    R.sub.3 --NR.sub.4 --(CH.sub.2).sub.m COOR.sub.7           B- 13

    R.sub.3 --OC(O)CH.sub.2 CH[C(O)OR.sub.3 ]CH[C(O)OR.sub.3 ]CH.sub.2 C(O)O--R.sub.3                                            B- 14

    R.sub.3 --OC(O)(CH.sub.2).sub.n --CH.sub.3                 B- 15

    R.sub.3 OC(O)--Aryl                                        B-16

    (R.sub.3).sub.3 P                                          B-17

    (R.sub.3).sub.2 PR                                         B-18

    R.sub.3 PRR                                                B-19 ##STR8##  wherein R.sub.10 signifies hydrogen, C.sub.1-10 alkyl, C.sub.1-10 alkenyl

R signifies hydrogen, C₁₋₂₀ alkyl, alkoxy, --C(O)alkyl, --OC(O)alkyl or##STR9## wherein n is a integer selected from 1 to 19 ##STR10##

    R.sub.3 --O--CH═C(COOR.sub.3).sub.2                    B- 24

The ratio of component A to component B can be chosen within widelimits. However, a synergistic effect has been observed when the A to Bratios are 95:5 to 5:95, preferably 75:25 to 25:75, more preferably65:35 to 35:65.

The compounds of component A and of component B are known or may be madefrom known compounds by known methods. Further, in this specification,where a range is given, the figures defining the range are included. Anygroup capable of being linear, branched or cyclic is linear, branched orcyclic unless indicated to the contrary. Also in this specification,where a symbol appears more than once in a formula, its significancesare independent of one another unless indicated to the contrary.

In formula I R₁ signifies preferably C₁₋₈ alkyl, formyl, acetyl,propionyl, C₈ alkoxy.

R₂ in formula I signifies preferably methoxy.

In a preferred embodiment of the invention in formula I of component AR₁ signifies methyl and R₂ signifies methoxy.

In preferred compositions according to the invention component B isselected from a group consisting of the following compounds (1) to (6).

(1) a compound of formula B-1 wherein n is 8 and

R₃ signifies ##STR11## (2) a compound of formula B-1 wherein n is 8 andR₃ signifies ##STR12## (3) a compound of formula B-1 wherein n is 8 andR₃ signifies ##STR13## (4) a compound of formula B-10 wherein R₅signifies hydrogen and R₆ signifies (CH₂)_(m) COOR₇ wherein m is 2 andR₇ is a mixture of C₁₂ H₂₅ and C₁₄ H₂₉ in the ratio 60 to 40.

(5) a compound of formula B-10 wherein R₅ and R₆ signify hydrogen.

(6) a compound of formula B-15 wherein n is 11 to 17 and

R₃ signifies ##STR14##

Further, particularly useful compounds of component B are as listedbelow.

Bis(2,2,6,6-tetramethyl-4-piperidinyl)succinate

Bis(2,2,6,6-tetramethyl-4-piperidinyl)sebacate

Bis(1,2,2,6,6-pentamethyl-4-piperidinyl)sebacate

Bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl)succinate

Bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl)sebacate

Tetrakis(2,2,6,6-tetramethyl-4-piperidinyl)-1,2,3,4-butane-tetracarboxylate1,1'-(1,2-Ethanediyl)bis-(3,3,5,5-tetramethylpiperazinone)

1-N-Isopropyl-3,3,5,5-tetramethyl-2-piperazinone

2,2,6,6-Tetramethyl-4-piperidinylbenzoate

2,2,6,6-Tetramethyl-4-piperidinylstearate

Bis(1,2,2,6,6-pentamethyl-piperidyl)-2-^(n)butyl-2-(2-hydroxy-3,5-di^(tert) butyl-benzyl)malonate

3-^(n) Octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione

8-Acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione

3-Dodecyl-1-(2',2',6',6'-tetramethyl-4'-piperidyl)-pyrrolidin-2,5-dione

3-Dodecyl-1-(1',2',2',6',6'-pentamethyl-4'-piperidyl)-pyrrolidin-2,5-dione

3-Dodecyl-1-(1'-acetyl-2',2',6',6'-tetramethyl-4'-piperidyl)-pyrrolidin-2,5-dione

N-(2,2,6,6-tetramethyl-4-piperidinyl)-glycine-(C₁ -C₂₀)alkylester

N,N'-1,6-Hexanediylbis[N-(2,2,6,6-tetramethyl-4-piperidinyl)-formamide]

Hexahydro-2,6-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1H,4H,5H,8H-2,3a,4a,6,7a,8a-hexaazacyclopenta[def]fluorene-4,8-dione

2,2,4,4-Tetramethyl-7-oxa-3,20-diaza-dispiro[5.1.11.2]heneicosan-21-on

2,2,4,4-Tetramethyl-7-oxa-3,20-diaza-dispiro[5.1.11.2]heneicosan-21-on-20-propanoicacid dodecyl ester

1,5-Dioxaspiro[5.5]undecane-3,3-dicarboxylic acidbis(2,2,6,6-tetramethyl-4-piperidinyl)-ester

1,5-Dioxaspiro[5.5]undecane-3,3-dicarboxylic acidbis(1,2,2,6,6-pentamethyl-4-piperidinyl)-ester

1,5-Dioxaspiro[5.5]undecane-3,3-dicarboxylic acidbis(1-acetyl-2,2,6,6-tetra-methyl-4-piperidinyl)-ester

Tris(1,2,2,6,6-pentamethyl-4-piperidinyl)phosphite2-Methyl-2(2",2",6",6"-tetramethyl-4"-piperidinylamino)-N-(2',2',6',6'-tetra-methyl-4'-piperidinyl)propionylamide

Glycine-N,N-bis[2-oxo-2-[(2,2,6,6-tetramethyl-4-piperidinyl)-oxy]ethyl]-2,2,6,6-tetramethyl-4-piperidinylester

1-[2-(3,5-Di^(tert)butyl-4-hydroxyphenylpropionyloxy)ethyl]-4-(3,5-di^(tert)butyl-4-hydroxyphenylpropionyloxy)-2,2,6,6-tetramethylpiperidine

Pentakis(2,2,6,6-tetramethyl-4-piperidyl)diethylenetriamine-N,N,N',N",N"-pentaacetate

According to the present invention, there is further provided a solidmasterbatch composition comprising novel stabilizer compositions ashereinabove described. In such masterbatch compositions usually theamount of the stabilizer composition according to the invention is 10 to80% by weight, preferably 15 to 40% by weight and the amount of thenatural or synthetic polymeric or prepolymeric material which isidentical to or compatible with the natural or synthetic polymeric orprepolymeric substrate to be stabilized is 90 to 20% by weight,preferably 85 to 60% by weight.

The invention further provides a process for enhancing the lightstability of natural or synthetic polymeric or prepolymeric substrates,comprising the incorporation therein of a stabilizing quantity of astabilizer composition as hereinabove described as such or in form of asolid masterbatch composition. The quantity of composition needed toconfer an appreciable extent of light stabilization on a substratevaries with the type and end-use of the substrate. The skilled personcan readily ascertain the appropriate quantity for any given case, buttypical quantities are from 0.01 to 7.5% by weight, preferably from 0.03to 5% by weight, more preferably 0.2 to 3.5% by weight.

The stabilizer composition according to the invention may beincorporated by known methods into the substrate to be stabilized beforeor after the polymerization, for example by melt-mixing, if appropriatewith further additives before or during the shaping process, or byapplying the dissolved or dispersed stabilizer composition on to thesubstrate, if appropriate with subsequent evaporation of the solvent.

The invention further provides a stabilized organic material comprisinga light-stabilizing quantity of a composition as hereinabove describedand a natural or synthetic polymeric or prepolymeric substrate. Thissubstrate or the stabilized organic material is subjected to a shapingprocess, as mentioned above, which comprises the production of the wholegamut of polymeric articles, for example fibers, yarn, fabric, moldings,foam, coatings, lacquers, varnishes or adhesives.

Examples of the substrate to be stabilized are:

1. Polymers of monoolefins and diolefins, for example polypropylene,polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyisoprene orpolybutadiene, as well as polymers of cycloolefins, for instance ofcyclopentene or norbornene, polyethylene (which optionally can becrosslinked), for example high density polyethylene (HDPE), low densitypolyethylene (LDPE), linear low density polyethylene (LLDPE), branchedlow density polyethylene (BLDPE).

Polyefins, i.e. the polymers of monoolefins exemplified in the precedingparagraph, preferably polyethylene and polypropylene, can be prepared bydifferent, and especially by the following methods:

a) radical polymerization (normally under high pressure and at elevatedtemperature)

b) catalytic polymerization using a catalyst that normally contains oneor more than one metal of groups IVb, Vb, VIb or VIII of the PeriodicTable. These metals usually have one or more than one ligand, typicallyoxides, halides, alcoolates, esters, ethers, amines, alkyls, alkenylsand/or aryls that may be either π- or σ-coordinated. These metalcomplexes may be in the free form or fixed on substrates, typically onactivated magnesium chloride, titanium(III)-chloride, alumina or siliconoxide. These catalysts may be soluble or insoluble in the polymerizationmedium. The catalysts can be used themselves in the polymerization orfurther activators may be used, typically metal alkyls, metal hydrides,metal alkyl halides, metal alkyl oxides or metal alkyloxanes, saidmetals being elements of groups Ia, Iia and/or IIIa of the PeriodicTable. The activators may be modified conveniently with further ester,ether, amine or silyl ether groups. These catalyst systems are usuallytermed Philips, Standard Oil Indiana, Ziegler(-Natta), TNZ (DuPont),metallocene or single site catalysts (SSC).

2. Mixtures of the polymers mentioned under 1), for example mixtures ofpolypropylene with polyisobutylene, polypropylene with polyethylene (forexample PP/HDPE, PP/LDPE) and mixtures of different types ofpolyethylene (for example LDPE/HDPE).

3. Copolymers of monoolefins and diolefins with each other vinylmonomers, for example ethylene/propylene copolymers, linear low densitypolyethylene (LLDPE) and mixtures thereof with low density polyethylene(LDPE), propylene/but-1-ene copolymers, propylene/isobutylenecopolymers, ethylene/but-1-ene copolymers, ethylene/hexene copolymers,ethylene/methylpentene copolymers, ethylene/heptene copolymers,ethylene/octene copolymers, propylene/butadiene copolymers,isobutylene/isoprene copolymers, ethylene/alkyl acrylate copolymers,ethylene/alkyl methacrylate copolymers, ethylene/vinyl acetatecopolymers and their copolymers with carbon monoxide or ethylene/acrylicacid copolymers and their salts (ionomers) as well as terpolymers ofethylene with propylene and a diene such as hexadiene, dicyclopentadieneor ethylidenenorbornene; and mixtures of such copolymers with oneanother and with polymers mentioned in 1) above, for examplepolypropylene/ethylenepropylene copolymers, LDPE/ethylenevinyl acetatecopolymers (EVA), LDPE/ethyleneacrylic acid copolymers (EAA), LLDPE/EVA,LLDPE/EAA and alternating or random polyalkylene/carbon monoxidecopolymers and mixtures thereof with other polymers, for examplepolyamides.

4. Hydrocarbon resins (for example C₅ -C₉) including hydrogenatedmodifications thereof (e.g. tackifiers) and mixtures of polyalkylenesand starch.

5. Polystyrene, poly(p-methylstyrene), poly(α-methylstyrene).

6. Copolymers of styrene or α-methylstyrene with dienes or acrylicderivatives, for example styrene/butadiene, styrene/acrylonitrile,styrene/alkyl methacrylate, styrene/butadiene/alkyle acrylate,styrene/butadiene/alkyl methacrylate, styrene/maleic anhydride,styrene/acrylonitrile/methyl acrylate: mixtures of high impact strengthof styrene copolymers and another polymer, for example a polyacrylate, adiene polymer or an ethylene/propylene/diene terpolymer, and blockcopolymers of styrene such as styrene/butadiene/styrene,styrene/isoprene/styrene, styrene/ethylene/styrene orstyrene/ethylene/propylene/styrene.

7. Graft copolymers of styrene or α-methylstyrene, for example styreneon polybutadiene, styrene on polybutadiene-styrene orpolybutadiene-acrylonitrile copolymers: styrene and acrylonitrile (ormethacrylonitrile) on polybutadiene: styrene, acrylonitrile and methylmethacrylate on polybutadiene: styrene and maleic anhydride onpolybutadiene: styrene, acrylonitrile and maleic anhydride or maleimideon polybutadiene: styrene and maleimide on polybutadiene: styrene andalkyl acrylates or methacrylates on polybutadiene: styrene andacrylonitrile on ethylene/polypropylene/diene terpolymers; styrene andacrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styreneand acrylonitrile on acrylate/butadiene copolymers, as well as mixturesthereof with the copolymers listed under 6), for example the copolymermixtures known as ABS, MBS, ASA or AES polymers.

8. Halogen-containing polymers such as polychloroprene, chlorinatedrubbers, chlorinated or sulfochlorinated polyethylene, copolymers ofethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers,especially polymers of halogen-containing vinyl compounds, for examplepolyvinyl chloride, polyvinyl-idene chloride, polyvinyl fluoride,polyvinylidene fluoride, as well as copolymers thereof such as vinylchloride/vinylidene chloride, vinyl chloride/vinyl acetate or vinylidenechloride/vinyl acetate copolymers.

9. Polymers derived from α,β-unsaturated acids and derivatives thereofsuch as polyacrylates and polymethacrylates; polymethyl methacrylates,polyacrylamides and polyacrylonitriles, impact-modified with butylacrylate.

10. Copolymers of the monomers mentioned under 9) with each other orwith other unsaturated monomers, for example acrylonitrile/butadienecopolymers, acryl-onitrile/alkyl acrylate copolymers,acrylonitrile/alkoxyalkyl acrylate or acryl-onitrile/vinyl halidecopolymers or acrylonitrile/alkyl methacrylate/butadiene terpolymers.

11. Polymers derived from unsaturated alcohols and amines or the acylderivatives or acetals thereof, for example polyvinyl alcohol, polyvinylacetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate,polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well astheir copolymers with olefins mentioned in 1) above.

12. Homopolymers and copolymers of cyclic ethers such as polyalkyleneglycols, polyethylene oxide, polypropylene oxide or copolymers thereofwith bisglycidyl ethers.

13. Polyacetals such as polyoxymethylene and those polyoxymethyleneswhich contain ethylene oxide as a comonomer, polyacetals modified withthermoplastic polyurethanes, acrylates or MBS.

14. Polyphenylene oxides and sulfides, and mixtures of polyphenyleneoxides with styrene polymers of polyamides.

15. Polyurethanes derived from hydroxyl-terminated polyethers,polyesters of polybutadienes on the one hand and aliphatic or aromaticpolyisocyanates on the other, as well as precursors thereof.

16. Polyamides and copolyamides derived from diamines and dicarboxylicacids and/or from aminocarboxylic acids or the corresponding lactams,for example polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12,4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides startingfrom m-xylene diamine and adipic acid; polyamides prepared fromhexamethylene-diamine and isophthalic or/and terephthalic acid and withor without an elastomer as modifier, for examplepoly-2,4,4-trimethylhexamethylene terephthalamide or poly-m-phenyleneisophthal-amide; and also block copolymers of the aforementionedpolyamides with polyolefins, olefin copolymers, ionomers or chemicallybonded or grafted elastomers; or with polyethers, e.g. with polyethyleneglycol, polypropylene glycol or polytetramethylene glycol; as well aspolyamides or copolyamides modified with EPDM or ABS; and polyamidescondensed during processing (RIM polyamide systems).

17. Polyureas, polyimides, polyamide-imides and polybenzimidazoles.

18. Polyesters derived from dicarboxylic acids and diols and /or fromhydroxycarboxylic acids or the corresponding lactones, for examplepolyethylene terephthalate, polybutylene terephthalate,poly-1,4-dimethylolcyclohexane terephthalate and polyhydroxybenzoates,as well as block copolyether esters derived from hydroxyl-terminatedpolyethers; and also polyesters modified with polycarbonates or MBS.

19. Polycarbonates and polyester carbonates.

20. Polysulfones, polyether sulfones and polyether ketones.

21. Crosslinked polymers derived from aldehydes on the one hand andphenols, ureas and melamines on the other hand, such asphenol/formaldehyde resins, urea/formaldehyde resins andmelamine/formaldehyde resins.

22. Drying and non-drying alkyd resins.

23. Unsaturated polyester resins derived from copolyesters of saturatedand unsaturated dicarboxylic acids with polyhydric alcohols and vinylcompounds as crosslinking agents, and also halogen containingmodifications thereof of low flammability.

24. Crosslinkable acrylic resins derived from substituted acrylates, forexample epoxy acrylates, urethane acrylates or polyester acrylates.

25. Alkyd resins, polyester resins and acrylate resins crosslinked withmelamine resins, urea resins, polyisocyanates or epoxy resins.

26. Crosslinked epoxy resins derived from polyepoxides, for example frombis-glycidyl ethers or from cycloaliphatic diepoxides.

27. Natural polymers such as cellulose, rubber, gelatin and chemicallymodified homologous derivatives thereof, for example cellulose acetates,cellulose propionates and cellulose butyrates, or the cellulose etherssuch as methyl cellulose; as well as resins and their derivatives.

28. Blends of the aforementioned polymers (polyblends), for examplePP/EPDM, Polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS,PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR,PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 andcopolymers, PA/HDPE, PA/PP, PA/PPO.

29. Naturally accruing and synthetic organic materials which are puremonomeric compounds or mixtures of such compounds, for example mineraloils, animal and vegetable fats, oil and waxes, or oils, fats and waxesbased on synthetic esters (e.g. phthalates, adipates, phosphates ortrimellitates) and also mixtures of synthetic esters with mineral oilsin any weight ratios, typically those used as spinning compositions, aswell as aqueous emulsions of such materials.

30. Aqueous emulsions of natural or synthetic rubber, e.g. natural latexof carboxylated styrene/butadiene copolymers.

Further additives, if appropriate, can be added. Examples are given inthe following.

1. Antioxidants

1.1 Alkylated monophenols, for example,2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol,2,6-di-tert-butyl-4-ethylphenol, 2s,6-di-tert-butyl-4-n-butylphenol,2,6-di-tert-butyl-4-isobutylphenol, 2,6-di-cyclopentyl-4-methylphenol,2-(α-methylcyclohexyl)-4,6-dimethylphenol,2,6-di-octadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol,2,6-di-tert-butyl-4-methoxy-methylphenol, 2,6-di-nonyl-4-methylphenol,2,4-di-methyl-6-(1'-methylunde-1'-yl)phenol,2,4-di-methyl-6-(1'-methyl-heptadec-1'-yl)phenol,2,4-dimethyl-6-(1'-methyltridec-1'-yl)phenol and mixtures thereof.

1.2 Alkylthiomethylphenols, for example,2,4-dioctylthiomethyl-6-tert-butylphenol,2,4-dioctylthiomethyl-6-methylphenol,2,4-dioctylthio-methyl-6-ethylphenol,2,6-di-dodecylthiomethyl-4-nonylphenol.

1.3 Hydroquinones and alkylated hydroquinones, for example,2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone,2,5-di-tert-amylhydro-quinone, 2,6-diphenyl-4-octadecyloxyphenol,2,6-di-tert-butylhydro-quinone, 2,5-di-tert-butyl-4-hydroxyanisole,3,5-di-tert-butyl-4-hydroxy-anisole, 3,5-di-tert-butyl-4-hydroxyphenylstearate, bis-(3,5-di-tert-butyl-4-hydroxyphenyl)adipate.

1.4 Tocopherols, for example, α-tocopherol, β-tocopherol, γ-tocopherol,δ-tocopherol and mixtures thereof (Vitamin E).

1.5 Hydroxylated thiophenyl ethers, for example,2,2'-thiobis(6-tert-butyl-4-methylphenol), 2,2'-thiobis(4-octylphenol),4,4'-thiobis(6-tert-butyl-3-methylphenol),4,4'-thiobis(6-tert-butyl-2-methylphenol),4,4'-thiobis(3,6-di-sec-amylphenol),4,4'-bis(2,6-dimethyl-4-hydroxyphenyl)-disulfide.

1.6 Alkylidenebisphenols, for example,2,2'-methylenebis(6-tert-butyl-4-methylphenol),2,2'-methylenebis(6-tert-butyl-4-ethylphenol),2,2'-methylenebis[4-methyl-6-(α-methylcyclohexyl)-phenol],2,2'-methyl-enebis(4-methyl-6-cyclohexylphenol,2,2'-methylenebis(6-nonyl-4-methylphenol),2,2'-methylenebis(4,6-di-tert-butylphenol),2,2'-ethyl-idenebis(4,6-di-tert-butylphenol),2,2'-ethylidenebis(6-tert-butyl-4-iso-butylphenol),2,2'-methylenebis[6-(α-methylbenzyl)-4-nonylphenol],2,2'-methylenebis[6-α,α-dimethylbenzyl)-4-nonylphenol],4,4'-methyl-enebis(2,6-di-tert-butylphenol),4,4'-methylenebis(6-tert-butyl-2-methyl-phenol),1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,2,6-bis-(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol,1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane,ethylene glyco bis[3,3-bis-(3'-tert-butyl-4'-hydroxyphenyl)butyrate],bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)dicyclopentadiene,bis-[2-(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate,1,1-bis-(3,5-di-methyl-2-hydroxyphenyl)butane,2,2-bis-(3,5-di-tert-butyl-4-hydroxy-phenyl)-propane,2,2-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutane,1,1,5,5-tetra-(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.

1.7 O-, N- and S-benzylcompounds, for example,3,5,3',5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether,octadecyl-4-hydroxy-3,5-dimethylbenzyl-mercaptoacetate,tris-(3,5-di-tert-butyl-4-hydroxybenzyl)amine,bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate,bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide,isooctyl-3,5-di-tert-butyl-4-hydroxy-benzylmercaptoacetate.

1.8 Hydroxybenzylated malonates, for example,dioctadecyl-2,2-bis-(3,5-di-tert-butyl-2-hydroxybenzyl)-malonate,di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)-malonate,di-dodecylmercaptoethyl-2,2-bis-(3,5-di-tert-butyl-4-hydroxybenzyl)-malonate,bis-[4-(1,1,3,3-tetramethyl-butyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.

1.9 Aromatic hydroxybenzyl compounds, for example,1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene,1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene,2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.

1.10 Triazine compounds, for example,2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis((3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine,2,4,6-tris-(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine,1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-di-methylbenzyl)isocyanurate,2,4,6-tris(3,5-di-tert-butyl-4-hydroxy-phenylethyl)-1,3,5-triazine,1,3,5-tris((3,5-di-tert-butyl-4-hydroxy-phenylpropionyl)hexahydro-1,3,5-triazine,1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate.

1.11 Benzylphosphonates, for example,dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate,diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphon-ate,dioctadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate,diocta-decyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, thecalcium salt of the monoethyl ester of3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.

1.12 Acylaminophenols, for example, 4-hydroxylauranilide,4-hydroxystear-anilide, octylN-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.

1.13 Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid withmono-or polyhydric alcohols, e.g., with methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neo-pentyl glycol, thiodiethylene glycol, triethyleneglycol, pentaerythritol, tris(hydroxyethyl) isocyanurate,N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol,trimethylhexanediol, trimethylol-propane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.14 Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acidwith mono- or polyhydric alcohols, e.g., with methanol, ethanol,octanol, octa-decanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, triethyleneglycol, pentaerythritol, tris(hydroxyethyl) isocyanurate,N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol,trimethylhexanediol, trimethylol-propane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.15 Esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid withmono- or polyhydric alcohols, e.g., with methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, triethyleneglycol, pentaerythritol, tris(hydroxyethyl) isocyanurate,N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol,trimethylhexanediol, tri-methylolpropane,4-hydroxymethyl-1-phospha-2,6,7 trioxabicyclo[2.2.2]-octane.

1.16 Esters of 3,5-di-tert-butyl-4-hydroxyphenyl acetic acid with mono-or polyhydric alcohols, e.g., with methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neo-pentyl glycol, thiodiethylene glycol, triethyleneglycol, pentaerythritol, tris(hydroxyethyl) isocyanurate,N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol,trimethylhexanediol, trimethylol-propane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.17 Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, e.g.N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylene-diamine,N, N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine.

2. UV absorbers and other light stabilizers

2.1 2-(2'-Hydroxyphenyl)benzotriazoles, for example,2-(2'-hydroxy-5'-methylphenyl)-benzotriazole,2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-benzotriazole,2-(5'-tert-butyl-2'-hydroxyphenyl)benzotriazole,2-(2'-hydroxy-5'-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole,2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-chloro-benzotriazole,2-(3'-tert-butyl-2'-hydroxy-5'-methylphenyl)5-chloro-benzotriazole,2-(3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl)benzotriazole,2-(2'-hydroxy-4'-octyloxyphenyl)-benzotriazole,2-(3',5'-di-tert-amyl-2'-hydroxyphenyl)benzotriazole,2-(3',5'-bis-(α,α-dimethylbenzyl)-2'-hydroxyphenyl)benzotriazole,2-(3'-tert-butyl-5'-α,α-dimethylbenzyl-2'-hydroxyphenyl)benzotriazole,mix-ture of2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)-5-chloro-benzotriazole,2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)-carbonyl-ethyl]-2'-hydroxyphenyl)-5-chloro-benzotriazole,2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)-5-chloro-benztriazole,2-(3'-tert-butyl-2'-hydroxy-5'(2-octyloxycarbonylethyl)phenyl)benzotri-azole,2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-2'-hydroxy-phenyl)benzotriazole,2-(3-dodecyl-2'-hydroxy-5'-methylphenyl)benzotri-azole, and2-(3'-tert-butyl-2'-hydroxy-5'-(2-isooctyloxycarbonylethyl)-phenylbenzotriazole,2,2'-methylene-bis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazole-2-ylphenol];the transesterification product of2-[3'-tert-butyl-5'(2-methoxycarbonylethyl)-2'-hydroxyphenyl]-2H-benzotriazolewith polyethyleneglycol 300; [R--CH₂ CH₂ --COO(CH₂)₃ ]₂ - whereR=3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazole-2-ylphenyl.

2.2 2-Hydroxybenzophenones, for example, the 4-hydroxy, 4-methoxy,4-octy-loxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxyand 2'-hydroxy-4,4'-dimethoxy derivatives.

2.3 Esters of substituted and unsubstituted benzoic acids, as forexample, 4-tert-butylphenyl-salicylate, phenyl-salicylate,octylphenyl-salicylate, di-benzoyl-resorcinol,bis(4-tert-butylbenzoyl)resorcinol, benzoyl resorcin-ol,2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate,hexa-decyl-3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl3,5-di-tert-butyl-4-hydroxybenzoate,2-methyl-4,6-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate.

2.4 Acrylates, for example, ethyl α-cyano-β,β-diphenylacrylate, isooctylα-cyano-β,β-diphenylacrylate, methyl α-carbomethoxycinnamate, methylα-cyano-β-methyl-p-methoxycinnamate, butylα-cyano-β-methyl-p-methoxy-cinnamate, methylα-carbomethoxy-p-methoxy-cinnamate andN-(β-carbomethoxy-β-cyanovinyl)-2-methylindoline.

2.5 Nickel compounds, for example, nickel complexes of2,2'-thio-bis-[4-(1,1,3,3-tetramethylbutyl)phenol], such as the 1:1 or1:2 complex, with or without additional ligands such as n-butylamine,triethanolamine or N-cyclohexyldiethenolamine, nickeldibutyldithiocarbamate, nickel salts of the monoalkyl esters, e.g. themethyl or ethyl ester of 4-hydroxy-3,5-di-tert-butyl-benzylphosphonicacid, nickel complexes of ketoximes, e.g. of 2-hydroxy-4-methylphenylundecylketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxyrazole,with or without additional ligands.

2.6 Oxamides, for example, 4,4'-dioctyloxyoxanilide,2,2'-diethoxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butoxanilide,2,2'-didodecyloxy-5,5'-di-tert-butoxanilide, 2-ethoxy-2'-ethyloxanilide,N,N'-bis(3-dimethylamino-propyl)oxanilide,2-ethoxy-5-tert-butyl-2'-ethoxanilide and its mixture with2-ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide and mixtures of ortho- andpara-methoxy-disubstituted oxanilides and mixtures of ortho- andpara-ethoxy-disubstituted oxanilides.

2.7 2-(2-Hydroxyphenyl)1,3,5-triazines, for example,2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis-(2,4-dimethylphenyl)-1,3,5-triazine,2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2,4-bis(2-hydroxy-4-propyloxy-phenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-dodecyl-oxyphenyl)-4,6-bis-(4-methylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyl-oxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-butyloxypropoxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine,2-[2-hy-droxy-4-(2-hydroxy-3-octyloxy-propyloxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine.

3. Metal deactivators, for example, N,N'-diphenyloxamide,N-salicylayl-N'-salicyloyl hydrazine, N,N'-bis(salicyloyl) hydrazine,N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine,3-salicyloylamino-1,2,4-triazole, bis-(benzylidene)oxalyl dihydrazide,oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydra-zide,N,N'-diacetyladipoyl dihydrazide, N,N'-bis-(salicyloyl)-oxalyldihydrazide, N,N'-bis(salicyloyl)-thiopropionyl dihydrazide.

4. Phosphites and phosphonites, for example, triphenyl phosphite,diphenyl alkyl phosphites, phenyl dialkyl phosphites,tris(nonylphenyl)phosphite, trilauryl phos-phite, trioctadecylphosphite, distearyl pentaerythritol diphosphite,tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritoldiphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite,bis-(2,6-di-tert-butyl-4-methylphenyl)-pentaerythritol diphosphite,diisodecyloxypentaerythritol diphosphite,bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite,bis(2,4,6-tris(tert-butyl-phenyl)pentaerythritol diphosphite, tristearylsorbitol triphosphite,tetrakis-(2,4-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite,6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz[d,g]-1,3,2-dioxaphosphocin,6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz-[d,g]-1,3,2-dioxaphosphocin,bis(2,4-di-tert-butyl-6-methylphenyl)methylphosphite,bis(2,4-di-tert-butyl-6-methylphenyl)ethyl-phos-phite.

5. Hydroxylamines, for example, dibenzoylhydroxylamine,dioctylhydroxylamine, diodecylhydroxylamine, ditetradecylhydroxylamine,dihexadecylhydroxylamine, dioctadecylhydroxylamine,1-hydroxy-2,2-6,6-tetramethyl-4-piperidyl benzoate orbis(1-hydroxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate.

6. Peroxide scavengers, for example, esters of β-thiodipropionic acids,for example the lauryl, stearyl, myristyl or tridecyl esters,mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, zincdibutyl-dithiocarbamate, dioctadecyl di-sulfide, pentaerythritoltetrakis(β-dodecylmercapto)propionate.

7. Polyamide stabilizers, for example, copper salts in combination withiodides and/or phosphorus compounds and salts of divalent manganese.

8. Basic co-stabilizers, for example, melamine, polyvinylpyrrolidine,dicyandiamide, triallyl cyanurate, urea derivatives, hydrazinederivatives, amines, polyamides, polyurethanes, alkali metal salts andalkaline earth metal salts of higher fatty acids, for example calciumstearate, zinc stearate, magnesium behenate, magnesium stearate, sodiumricinoleate and potassium palmitate, antimony pyrocatecholate or tinpyrocatecholate.

9. Nucleating agents, for example, 4-tert-butylbenzoic acid, adipicacid, diphenyl-acetic acid.

10. Fillers or reinforcing agents, for example, calcium cabonate,silicates, glass fibers, asbestos, talc, kaolin, mica, barium sulfate,metal oxides and hydroxides, carbon black, graphite.

11. Other additives, for example, plasticisers, lubricants, emulsifiers,pigments, optical brighteners, flameproofing agents, antistatic agentsand blowing agents.

12. Benzofuranones and indolinones, for example, those disclosed in U.S.Pat. No. 4,325,863, U.S. Pat. No. 4,338,244, U.S. Pat. No. 5,175,312,U.S. Pat. No. 5,216,052, U.S. Pat. No. 5,252,643, DE-A-4 316 611, DE-A-4316 622, DE-A-4 316 876, EP-A-0 589 839 or EP-A-0 591 102 or3-[4-(2-acetoxyethoxy)phenyl]-5,7-di-tert-butyl-benzofuran-2-one,5,7-di-tert-butyl-3-[4-2-stearoyloxyethoxy)phenyl]-benzofuran-2-one,3,3'-bis-[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one],5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one,3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one,3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butyl-benzofuran-2-one.

The invention is further illustrated by means of the following examplesin which all parts are expressed by weight:

EXAMPLE 1

100 parts of polypropylene powder (melt flow index 4, 230° C./2.16 kg)are dry blended with 0.1 parts Ca-stearate, 0.05 parts ofpentaerythrityl-tetrakis-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate]and 0.075 parts of each component A and component B and are homogenizedfor 10 minutes at 220° C. The composition thus obtained iscompression-molded in a toggle press to give a 1-1.5 mm thick plate.Part of the crude molding obtained is cut out and compressed between twohigh gloss hard aluminium foils at 210° C. for 1.5 minutes at a pressureof 3 tons and additionally for further 1.5 minutes at a pressure of 30tons to give a 0.0 mm thick film. Portions each of about 40×45 mm arenow punched from this film and irradiated in Atlas Weather-Ometer Ci 65.At regular intervals of time, these test samples are removed from theirradiation apparatus and tested for their carbonyl content in an IRspectro-photometer. The increase in the carbonyl extinction on exposureis a measure of the photooxidative degradation of the polymer and,according to experience, is associated with a deterioration in themechanical properties of the polymer. The time taken to reach acarbonyl-index of 0.30 is considered to be a measure of the stabilizingaction.

    ______________________________________                                        Composition No.                                                                            Component A   Component B                                        ______________________________________                                        A            Sanduvor PR 31 .sup.(1)                                                                     Tinuvin 770 .sup.(2)                               B            Sanduvor PR 31                                                                              Tinuvin 292 .sup.(3)                               C            Sanduvor PR 31                                                                              Tinuvin 123 .sup.(4)                               D            Sanduvor PR 31                                                                              Sanduvor 3050 .sup.(5)                             E            Sanduvor PR 31                                                                              Dastib 845 .sup.(6)                                ______________________________________                                    

1) Sanduvor PR 31 is a trade name of the company Clariant for a compoundof formula I wherein R₁ signifies methyl and R₂ signifies methoxy.

2) Tinuvin 770 is a trade name of the company Ciba-Geigy for a compoundof formula B-1 wherein n is 8 and R₃ signifies ##STR15##

3) Tinuvin 292 is a trade name of the company Ciba-Geigy for a compoundof formula B-1 wherein n is 8 and R₃ signifies ##STR16##

4) Tinuvin 123 is a trade name of the company Ciba-Geigy for a compoundof formula B-1 wherein n is 8 and R₃ signifies ##STR17##

5) Sanduvor 3050 is a trade name of the company Clariant for a compoundof formula B-10 wherein R₅ signifies hydrogen and R₆ signifies (CH₂)_(m)COOR₇ wherein m is 2 and R₇ is a mixture of C₁₂ H₂₅ and C₁₄ H₂₉ in theratio of 60 to 40.

6) Dastib is a trade name of the company Vucht for a compound of formulaB-15 wherein m is 11 to 17 and R₃ signifies ##STR18##

EXAMPLE 2

100 parts of polypropylene powder (Hostalen PPU 0180 P, Hoechst, MFI 15g/10 min.; 230° C./2.16 kg) are mixed with 0.1 parts Ca-stearate, 0.05partspentaerythrityl-tetrakis-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate]and 0.15 parts of the light stabilizers and melt-homogenized byextrusion.

Accelerated weathering was done according to the following standards:

UV-A: according to ASTM D-5208 (UVCON-device)

CAM-7: according to DIN 53387-A (Weather-Ometer Ci65)

Some of the plaques are used to produce press films of an averagethickness of about 0.1 mm. These films are also submitted to acceleratedweathering. Monitoring the increase of the carbonyl absorption at about1720 cm⁻¹ using an IR-spectrometer at certain time intervals gives anindication of the photooxidative degradation.

The time (T₀.5 measured) to reach the carbonyl extinction of 0.5 isgiven in tables 1 and 2.

The T₀.5 calculated -values are calculated according to the additivityrule (B. Ranby and J. F. Rabek, Photodegradation, Photo-oxidation andPhotostabilization of Polymers, Principles and Applications, aWiley-Interscience Publication, 1975, pp 418-422) and using thefollowing equation: ##EQU1##

The synergistic effect is determined comparing the calculated andmeasured T₀.5 -values. The values are also given in tables 1 and 2.

A synergistic effect for the described mixtures is given if T₀.5measured >T₀.5 calculated.

                  TABLE 1                                                         ______________________________________                                        Light stability in polypropylene films after UV-A irradiation                 HALS              T.sub.0.5 measured                                                                       T.sub.0.5 calculated                             ______________________________________                                        control                305                                                    0.15%   Sanduvor PR-31                                                                              1775                                                    0.15%   Tinuvin 770   3060                                                    0.15%   Tinuvin 292   2040                                                    0.15%   Tinuvin 123   1920                                                    0.15%   Sanduvor 3050 1570                                                    0.15%   Dastib 845    2900                                                    0.05%   Sanduvor PR-31                                                        0.10%   Tinuvin 770   2950       2630                                         0.05%   Sanduvor PR-31                                                                              2400       1950                                         0.10%   Tinuvin 292                                                           0.05%   Sanduvor PR-31                                                                              1930       1870                                         0.10%   Tinuvin 123                                                           0.05%   Sanduvor PR-31                                                                              1700       1630                                         0.10%   Sanduvor 3050                                                         0.10%   Sanduvor PR-31                                                                              2670       2150                                         0.05%   Dastib 845                                                            ______________________________________                                    

                  TABLE 2                                                         ______________________________________                                        Light stability in polypropylene films after Weather-Ometer CAM-7             irradiation                                                                   HALS              T.sub.0.5 measured                                                                       T.sub.0.5 calculated                             ______________________________________                                        control                520                                                    0.15%   Sanduvor PR-31                                                                              2470                                                    0.15%   Tinuvin 770   2500 (broken)                                           0.15%   Tinuvin 292   2320                                                    0.15%   Tinuvin 123   2090                                                    0.15%   Sanduvor 3050 2140                                                    0.15%   Dastib 845    2200                                                    0.05%   Sanduvor PR-31                                                                              2880       1667                                         0.10%   Tinuvin 770                                                           0.10%   Sanduvor PR-31                                                                              3100       2480                                         0.05%   Tinuvin 770                                                           0.05%   Sanduvor PR-31                                                                              2620       2370                                         0.10%   Tinuvin 292                                                           0.05%   Sanduvor PR-31                                                                              2550       2216                                         0.10%   Tinuvin 123                                                           0.05%   Sanduvor PR-31                                                                              2600       2250                                         0.10%   Sanduvor 3050                                                         ______________________________________                                    

What is claimed is:
 1. A composition consisting of a photoreactive, UVlight absorbing, low molecular weight polyalkylpiperidine of formula Ias component A ##STR19## wherein R₁ is hydrogen, hydroxyl, C₁₋₂₀ alkyl,C₁₋₂₀ alkoxy, or acyl, andR₂ is hydrogen, C₁₋₈ alkyl, or C₁₋₂ alkoxy,anda non-photoreactive, low molecular weight sterically hinderedpolyalkyl-piperidine as component B wherein component B is a compound offormula:

    R.sub.3 --OC(O)--(CH.sub.2).sub.n --C(O)O--R.sub.3         B- 1;

    R.sub.3 --NH--(CH.sub.2).sub.n --NH--R.sub.3               B- 2;

    R.sub.3 --OCH.sub.2 CH═CHCH.sub.2 --O--R.sub.3         B- 3;

    R.sub.3 --OC(O)--NR.sub.3 --(CH.sub.2).sub.6 --NR.sub.3 C(O)O--R.sub.3B- 4;

    R.sub.3 --O--Si(CH.sub.3).sub.2 --O--R.sub.3               B- 5;

wherein R₃ is a group selected from the group consisting of: ##STR20##wherein Alkyl is linear or branched or cyclic saturated C₁₋₁₈ alkylgroup or linear or branched or cyclic C₁₋₁₈ unsaturated group (alkenylgroup),n is an integer from 0 to 20; ##STR21## wherein R₄ is hydrogen,C₁₋₂₀ alkyl, or R₃ ; ##STR22## wherein X is oxygen or N--R₄, ##STR23##wherein R₅ is hydrogen, C₁₋₂₀ alkyl, hydroxyl, C₁₋₂₀ alkoxy, or acyl, R₆is hydrogen, C₁₋₂₀ alkyl, ##STR24## or (CH₂)_(m) COOR₇, wherein m is aninteger selected from 0 to 10, R₇ is C₁₋₂₀ alkyl; ##STR25##

    R.sub.3 --NH--C(O)--(CH.sub.2).sub.n --C(O)--NH--R.sub.3   B- 12;

    R.sub.3 --NR.sub.4 --(CH.sub.2).sub.m COOR.sub.7           B- 13;

    R.sub.3 --OC(O)CH.sub.2 CH[C(O)OR.sub.3 ]CH[C(O)OR.sub.3 ]CH.sub.2 C(O)O--R.sub.3                                            B- 14;

    R.sub.3 --OC(O)(CH.sub.2).sub.n --CH.sub.3                 B- 15;

    R.sub.3 OC(O)--Aryl                                        B-16;

    (R.sub.3).sub.3 P                                          B-17;

    (R.sub.3).sub.2 PR                                         B-18;

    R.sub.3 PRR                                                B-19; ##STR26##  wherein R.sub.10 is hydrogen, C.sub.1-10 alkyl, or C.sub.1-10 alkenyl,

R is hydrogen, C₁₋₂₀ alkyl, alkoxy, --C(O)alkyl, --OC(O)alkyl or##STR27## wherein n is an integer from 1 to 19; ##STR28## or

    R.sub.3 --O--CH═C(COOR.sub.3).sub.2                    B-
 24.


2. The composition according to claim 1, wherein n of formulae B-1 andB-2 is an integer from 1 to
 14. 3. The composition according to claim 2,wherein n of formulae B-1 and B-2 is an integer from 1 to
 10. 4. Thecomposition according to claim 1, wherein R₄ of formula B-6 is C₁₋₁₀alkyl.
 5. The composition according to claim 4, wherein R₄ of formulaB-6 is C₁₋₄ alkyl.
 6. The composition according to claim 1, wherein m of(CH₂)_(m) COOR₇ is an integer from 0 to
 2. 7. The composition accordingto claim 1, wherein A and B are in a ratio of A to B of 95:5 to 5:95. 8.The composition according to claim 7, wherein the ratio of A to B is75:25 to 25:75.
 9. The composition according to claim 8, wherein theratio of A to B is 65:35 to 35:65.
 10. A solid masterbatch compositioncomprising:(a) a composition consisting of a photoreactive, UV lightabsorbing, low molecular weight polyalkylpiperidine of formula I ascomponent A ##STR29## wherein R₁ is hydrogen, hydroxyl, C₁₋₂₀ alkyl,C₁₋₂₀ alkoxy, or acyl, andR₂ is hydrogen, C₁₋₈ alkyl, or C₁₋₂ alkoxy,anda non-photoreactive, low molecular weight sterically hinderedpolyalkyl-piperidine as component B wherein component B is a compound offormula:

    R.sub.3 --OC(O)--(CH.sub.2).sub.n --C(O)O--R.sub.3         B- 1;

    R.sub.3 --NH--(CH.sub.2).sub.n --NH--R.sub.3               B- 2;

    R.sub.3 --OCH.sub.2 CH═CHCH.sub.2 --O--R.sub.3         B- 3;

    R.sub.3 --OC(O)--NR.sub.3 --(CH.sub.2).sub.6 --NR.sub.3 C(O)O--R.sub.3B- 4;

    R.sub.3 --O--Si(CH.sub.3).sub.2 --O--R.sub.3               B- 5;

whereinR₃ is a group selected from the group consisting of: ##STR30##wherein Alkyl is linear or branched or cyclic saturated C₁₋₁₈ alkylgroup or linear or branched or cyclic C₁₋₁₈ unsaturated group (alkenylgroup),n is an integer from 0 to 20; ##STR31## wherein R₄ is hydrogen,C₁₋₂₀ alkyl, or R₃ ; ##STR32## wherein X is oxygen or N--R₄, ##STR33##wherein R₅ is hydrogen, C₁₋₂₀ alkyl, hydroxyl, C₁₋₂₀ alkoxy, or acyl, R₆is hydrogen, C₁₋₂₀ alkyl, ##STR34## or (CH₂)_(m) COOR₇, wherein m is aninteger selected from 0 to 10, R₇ is C₁₋₂₀ alkyl, ##STR35##

    R.sub.3 --NH--C(O)--(CH.sub.2).sub.n --C(O)--NH--R.sub.3   B- 12;

    R.sub.3 --NR.sub.4 --(CH.sub.2).sub.m COOR.sub.7           B- 13;

    R.sub.3 --OC(O)CH.sub.2 CH[C(O)OR.sub.3 ]CH[C(O)OR.sub.3 ]CH.sub.2 C(O)O--R.sub.3                                            B- 14;

    R.sub.3 --OC(O)(CH.sub.2).sub.n --CH.sub.3                 B- 15;

    R.sub.3 OC(O)--Aryl                                        B-16;

    (R.sub.3).sub.3 P                                          B-17;

    (R.sub.3).sub.2 PR                                         B-18;

    R.sub.3 PRR                                                B-19; ##STR36##  wherein R.sub.10 is hydrogen, C.sub.1-10 alkyl, or C.sub.1-10 alkenyl,

R is hydrogen, C₁₋₂₀ alkyl, alkoxy, --C(O)alkyl, --OC(O)alkyl or##STR37## wherein n is an integer from 1 to 19; ##STR38## or

    R.sub.3 --O--CH═C(COOR.sub.3).sub.2                    B- 24,

and (b) a natural or synthetic polymeric or prepolymeric material whichis identical to or compatible with a natural or synthetic polymericsubstrate to be stabilized.
 11. The solid masterbatch compositionaccording to claim 10, comprising 10 to 80% by weight of the stabilizercomposition and 90 to 20% by weight of a natural or synthetic polymericor prepolymeric material.
 12. The solid masterbatch compositionaccording to claim 11, wherein the stabilizer composition is 15 to 40%by weight.
 13. The solid masterbatch composition according to claim 11,wherein the natural or synthetic polymeric or prepolymeric material is85 to 60% by weight.
 14. A process for stabilizing a natural orsynthetic polymeric or prepolymeric substrate against the damageeffected by light comprising adding to the substrate a stabilizingquantity of a composition wherein the composition consists of aphotoreactive, UV light absorbing, low molecular weightpolyalkylpiperidine of formula I as component A ##STR39## wherein R₁ ishydrogen, hydroxyl, C₁₋₂₀ alkyl, C₁₋₂₀ alkoxy, or acyl, andR₂ ishydrogen, C₁₋₈ alkyl, or C₁₋₂ alkoxy,and a non-photoreactive, lowmolecular weight sterically hindered polyalkyl-piperidine as component Bwherein component B is a compound of formula:

    R.sub.3 --OC(O)--(CH.sub.2).sub.n --C(O)O--R.sub.3         B- 1;

    R.sub.3 --NH--(CH.sub.2).sub.n --NH--R.sub.3               B- 2;

    R.sub.3 --OCH.sub.2 CH═CHCH.sub.2 --O--R.sub.3         B- 3;

    R.sub.3 --OC(O)--NR.sub.3 --(CH.sub.2).sub.6 --NR.sub.3 C(O)O--R.sub.3B- 4;

    R.sub.3 --O--Si(CH.sub.3).sub.2 --O--R.sub.3               B- 5;

wherein R₃ is a group selected from the group consisting of: ##STR40##wherein Alkyl is linear or branched or cyclic saturated C₁₋₁₈ alkylgroup or linear or branched or cyclic C₁₋₁₈ unsaturated group (alkenylgroup),n is an integer from 0 to 20; ##STR41## wherein R₄ is hydrogen,C₁₋₂₀ alkyl, or R₃ ; ##STR42## wherein X is oxygen or N--R₄, ##STR43##wherein R₅ is hydrogen, C₁₋₂₀ alkyl, hydroxyl, C₁₋₂₀ alkoxy, or acyl, R₆is hydrogen, C₁₋₂₀ alkyl, ##STR44## or (CH₂)_(m) COOR₇, wherein m is aninteger selected from 0 to 10, R₇ is C₁₋₂₀ alkyl; ##STR45##

    R.sub.3 --NH--C(O)--(CH.sub.2).sub.n --C(O)--NH--R.sub.3   B- 12;

    R.sub.3 --NR.sub.4 --(CH.sub.2).sub.m COOR.sub.7           B- 13;

    R.sub.3 --OC(O)CH.sub.2 CH[C(O)OR.sub.3 ]CH[C(O)OR.sub.3 ]CH.sub.2 C(O)O--R.sub.3                                            B- 14;

    R.sub.3 --OC(O)(CH.sub.2).sub.n --CH.sub.3                 B- 15;

    R.sub.3 OC(O)--Aryl                                        B-16;

    (R.sub.3).sub.3 P                                          B-17;

    (R.sub.3).sub.2 PR                                         B-18;

    R.sub.3 PRR                                                B-19; ##STR46##  wherein R.sub.10 is hydrogen, C.sub.1-10 alkyl, or C.sub.1-10 alkenyl,

R is hydrogen, C₁₋₂₀ alkyl, alkoxy, --C(O)alkyl, --OC(O)alkyl or##STR47## wherein n is an integer from 1 to 19; ##STR48## or

    R.sub.3 --O--CH═C(COOR.sub.3).sub.2                    B-
 24.


15. A process for stabilizing a natural or synthetic polymeric orprepolymeric substrate against the damage effected by light comprisingadding to the substrate a stabilizing quantity of a solid masterbatchcomposition wherein the solid masterbatch composition comprises:(a) acomposition consisting of a photoreactive, UV light absorbing, lowmolecular weight polyalkylpiperidine of formula I as component A##STR49## wherein R₁ is hydrogen, hydroxyl, C₁₋₂₀ alkyl, C₁₋₂₀ alkoxy,or acyl, andR₂ is hydrogen, C₁₋₈ alkyl, or C₁₋₂ alkoxy,and anon-photoreactive, low molecular weight sterically hinderedpolyalkyl-piperidine as component B wherein component B is a compound offormula:

    R.sub.3 --OC(O)--(CH.sub.2).sub.n --C(O)O--R.sub.3         B- 1;

    R.sub.3 --NH--(CH.sub.2).sub.n --NH--R.sub.3               B- 2;

    R.sub.3 --OCH.sub.2 CH═CHCH.sub.2 --O--R.sub.3         B- 3;

    R.sub.3 --OC(O)--NR.sub.3 --(CH.sub.2).sub.6 --NR.sub.3 C(O)O--R.sub.3B- 4;

    R.sub.3 --O--Si(CH.sub.3).sub.2 --O--R.sub.3               B- 5;

whereinR₃ is a group selected from the group consisting of: ##STR50##wherein Alkyl is linear or branched or cyclic saturated C₁₋₁₈ alkylgroup or linear or branched or cyclic C₁₋₁₈ unsaturated group (alkenylgroup),n is an integer from 0 to 20; ##STR51## wherein R₄ is hydrogen,C₁₋₂₀ alkyl, or R₃ ; ##STR52## wherein X is oxygen or N--R₄, ##STR53##wherein R₅ is hydrogen, C₁₋₂₀ alkyl, hydroxyl, C₁₋₂₀ alkoxy, or acyl, R₆is hydrogen, C₁₋₂₀ alkyl, ##STR54## or (CH₂)_(m) COOR₇, wherein m is aninteger selected from 0 to 10, R₇ is C₁₋₂₀ alkyl; ##STR55##

    R.sub.3 --NH--C(O)--(CH.sub.2).sub.n --C(O)--NH--R.sub.3   B- 12;

    R.sub.3 --NR.sub.4 --(CH.sub.2).sub.m COOR.sub.7           B- 13;

    R.sub.3 --OC(O)CH.sub.2 CH[C(O)OR.sub.3 ]CH[C(O)OR.sub.3 ]CH.sub.2 C(O)O--R.sub.3                                            B- 14;

    R.sub.3 --OC(O)(CH.sub.2).sub.n --CH.sub.3                 B- 15;

    R.sub.3 OC(O)--Aryl                                        B-16;

    (R.sub.3).sub.3 P                                          B-17;

    (R.sub.3).sub.2 PR                                         B-18;

    R.sub.3 PRR                                                B-19; ##STR56##  wherein R.sub.10 is hydrogen, C.sub.1-10 alkyl, or C.sub.1-10 alkenyl,

R is hydrogen, C₁₋₂₀ alkyl, alkoxy, --C(O)alkyl, --OC(O)alkyl or##STR57## wherein n is an integer from 1 to 19; ##STR58## or

    R.sub.3 --O--CH═C(COOR.sub.3).sub.2                    B- 24,

and (b) a natural or synthetic polymeric or prepolymeric material whichis identical to or compatible with a natural or synthetic polymericsubstrate to be stabilized.
 16. The process according to claim 14,wherein 0.01 to 7.5% by weight of the composition is added.
 17. Theprocess according to claim 15, wherein 0.01 to 7.5% by weight of thecomposition is added.
 18. The process according to claim 16, wherein0.03 to 5% by weight of the composition is added.
 19. The processaccording to claim 18, wherein 0.2 to 3.5% by weight of the compositionis added.
 20. The process according to claim 17, wherein 0.03 to 5% byweight of the composition is added.
 21. The process according to claim20, wherein 0.2 to 3.5% by weight of the composition is added.
 22. Astabilized organic material comprising:(a) a composition consisting of aphotoreactive, UV light absorbing, low molecular weightpolyalkylpiperidine of formula I as component A ##STR59## wherein R₁ ishydrogen, hydroxyl, C₁₋₂₀ alkyl, C₁₋₂₀ alkoxy, or acyl, andR₂ ishydrogen, C₁₋₈ alkyl, or C₁₋₂ alkoxy,and a non-photoreactive, lowmolecular weight sterically hindered polyalkyl-piperidine as component Bwherein component B is a compound of formula:

    R.sub.3 --OC(O)--(CH.sub.2).sub.n --C(O)O--R.sub.3         B- 1;

    R.sub.3 --NH--(CH.sub.2).sub.n --NH--R.sub.3               B- 2;

    R.sub.3 --OCR.sub.2 CH═CHCH.sub.2 --O--R.sub.3         B- 3;

    R.sub.3 --OC(O)--NR.sub.3 --(CH.sub.2).sub.6 --NR.sub.3 C(O)O--R.sub.3B- 4;

    R.sub.3 --O--Si(CH.sub.3).sub.2 --O--R.sub.3               B- 5;

whereinR₃ is a group selected from the group consisting of: ##STR60##wherein Alkyl is linear or branched or cyclic saturated C₁₋₈ alkyl groupor linear or branched or cyclic C₁₋₁₈ unsaturated group (alkenylgroup),n is an integer from 0 to 20; ##STR61## wherein R₄ is hydrogen,C₁₋₂₀ alkyl, or R₃ ; ##STR62## wherein X is oxygen or N--R₄, ##STR63##wherein R₅ is hydrogen, C₁₋₂₀ alkyl, hydroxyl, C₁₋₂₀ alkoxy, or acyl, R₆is hydrogen, C₁₋₂₀ alkyl, ##STR64## or (CH₂)_(m) COOR₇, wherein m is aninteger selected from 0 to 10, R₇ is C₁₋₂₀ alkyl; ##STR65##

    R.sub.3 --NH--C(O)--(CH.sub.2).sub.n --C(O)--NH--R.sub.3   B- 12;

    R.sub.3 --NR.sub.4 --(CH.sub.2).sub.m COOR.sub.7           B- 13;

    R.sub.3 --OC(O)CH.sub.2 CH[C(O)OR.sub.3 ]CH[C(O)OR.sub.3 ]CH.sub.2 C(O)O--R.sub.3                                            B- 14;

    R.sub.3 --OC(O)(CH.sub.2).sub.n --CH.sub.3                 B- 15;

    R.sub.3 OC(O)--Aryl                                        B-16;

    (R.sub.3).sub.3 P                                          B-17;

    (R.sub.3).sub.2 PR                                         B-18;

    R.sub.3 PRR                                                B-19; ##STR66##  wherein R.sub.10 is hydrogen, C.sub.1-10 alkyl, or C.sub.1-10 alkenyl,

R is hydrogen, C₁₋₂₀ alkyl, alkoxy, --C(O)alkyl, --OC(O)alkyl or##STR67## wherein n is an integer from 1 to 19; ##STR68## or

    R.sub.3 --O--CH═C(COOR.sub.3).sub.2                    B- 24;

and (b) a natural or prepolymeric substrate.
 23. A method of using astabilized organic material in the production of fibers, yam, moldings,foamed plastic, coatings, lacquers, varnishes, adhesives, and fabriccomprising shaping the stabilized organic material wherein thestabilized organic material comprises:(a) a composition consisting of aphotoreactive, UV light absorbing, low molecular weightpolyalkylpiperidine of formula I as component A ##STR69## wherein R₁ ishydrogen, hydroxyl, C₁₋₂₀ alkyl, C₁₋₂₀ alkoxy, or acyl, andR₂ ishydrogen, C₁₋₈ alkyl, or C₁₋₂ alkoxy,and a non-photoreactive, lowmolecular weight sterically hindered polyalkyl-piperidine as component Bwherein component B is a compound of formula:

    R.sub.3 --OC(O)--(CH.sub.2).sub.n --C(O)O--R.sub.3         B- 1;

    R.sub.3 --NH--(CH.sub.2).sub.n --NH--R.sub.3               B- 2;

    R.sub.3 --OCH.sub.2 CH═CHCH.sub.2 --OR.sub.3           B- 3;

    R.sub.3 --OC(O)--NR.sub.3 --(CH.sub.2).sub.6 --NR.sub.3 C(O)O--R.sub.3B- 4;

    R.sub.3 --O--Si(CH.sub.3).sub.2 --O--R.sub.3               B- 5;

whereinR₃ is a group selected from the group consisting of: ##STR70##wherein Alkyl is linear or branched or cyclic saturated C₁₋₈ alkyl groupor linear or branched or cyclic C₁₋₁₈ unsaturated group (alkenylgroup),n is an integer from 0 to 20; ##STR71## wherein R₄ is hydrogen,C₁₋₂₀ alkyl, or R₃ ; ##STR72## wherein X is oxygen or N--R₄, ##STR73##wherein R₅ is hydrogen, C₁₋₂₀ alkyl, hydroxyl, C₁₋₂₀ alkoxy, or acyl, R₆is hydrogen, C₁₋₂₀ alkyl, ##STR74## or (CH₂)_(m) COOR₇, wherein m is aninteger selected from 0 to 10, R₇ is C₁₋₂₀ alkyl; ##STR75##

    R.sub.3 --NH--C(O)--(CH.sub.2).sub.n --C(O)--NH--R.sub.3   B- 12;

    R.sub.3 --NR.sub.4 --(CH.sub.2).sub.m COOR.sub.7           B- 13;

    R.sub.3 --OC(O)CH.sub.2 CH[C(O)OR.sub.3 ]CH[C(O)OR.sub.3 ]CH.sub.2 C(O)O--R.sub.3                                            B- 14;

    R.sub.3 --OC(O)(CH.sub.2).sub.n --CH.sub.3                 B- 15;

    R.sub.30 C(O)--Aryl                                        B-16;

    (R.sub.3).sub.3 P                                          B-17;

    (R.sub.3).sub.2 PR                                         B-18;

    R.sub.3 PRR                                                B-19; ##STR76##  wherein R.sub.10 is hydrogen, C.sub.1-10 alkyl, or C.sub.1-10 alkenyl,

R is hydrogen, C₁₋₂₀ alkyl, alkoxy, --C(O)alkyl, --OC(O)alkyl or##STR77## wherein n is an integer from 1 to 19; ##STR78## or

    R.sub.3 --O--CH═C(COOR.sub.3).sub.2                    B- 24;

and (b) a natural or prepolymeric substrate.